We report the preparation of triazatruxene-faced tetrahedral cage 1, which exhibits two diastereomeric configurations (T1 and T2) that differ in the handedness of the ligand faces relative to that of the octahedrally coordinated metal centers. At lower temperatures, T1 is favored, whereas T2 predominates at higher temperatures. Host-guest studies show that T1 binds small aliphatic guests, whereas T2 binds larger aromatic molecules, with these changes in binding preference resulting from differences in cavity size and degree of enclosure. Thus, by a change in temperature the cage system can be triggered to eject one bound guest and take up another.